Large pore zeolites with high silica to alumina ratios, i.e., of at least four, are desirable because of their particular catalytic selectivity and their thermal stability; the latter is a property particularly important when the zeolite is used as catalyst or in adsorption procedures wherein exposure to high temperatures would be expected. Although faujasite zeolites having silica to alumina ratios of less than four can be readily synthesized by a variety of methods, as disclosed, e.g., in U.S. Pat. Nos. 2,882,244 and 4,178,352, methods for preparing faujasite polymorphs of higher ratios generally involve several weeks of crystallization and result in poor yields of product, as reported by Kacirek, J. Phy. Chem., 79, 1589 (1975).
The use of quaternary ammonium salts as templates or reaction modifiers in the preparation of synthetic crystalline aluminosilicates (zeolites), first discovered by R. M. Barrer in 1961, has led to preparation of zeolites with high silica to alumina ratios which are not found in nature. A review provided by Barrer in Zeolites, Vol. I, p. 136 (October, 1981) shows the zeolite types which are obtained using various ammonium organic bases as cation. In addition, Breck, Zeolite Molecular Sieves, John Wiley (New York, 1974), pp. 348-378, provides a basic review of zeolites obtained using such ammonium cations in the synthesis thereof, as does a review by Lok et al. (Zeolites, 3, p. 282, 1983)).
The Si/Al ratios of a variety of readily synthesized NaY materials (SiO.sub.2 /Al.sub.2 O.sub.3 &lt;6) can be increased by a wide range of chemical or physical chemical treatments. However, these processes usually involve removal of Al from the zeolite framework and creation of a metastable defect structure, followed by filling the defects with Si from another part of the structure by further chemical treatments or hydrothermal annealing. Typical treatments use steam, e.g., U.S. Pat. No. 3,293,192; acid leaching, e.g., U.S. Pat. No. 3,506,400; treatments with EDTA, e.g., U.S. Pat. No. 4,093,560; treatment with SiCl.sub.4 (Beyer and Belenyakja, Catalysis by Zeolites S, p. 203 (1980), Elsevier Press.); treated with CHF.sub.3, i.e., 4,275,046; or treated with other chemicals. The products are often called "ultra stable" faujasites (cf. Maher and McDaniel Proceedings Intl. Conference on Molecular Sieves, London, 1967) because of their very high thermal and hydrothermal stability. However, such chemical processing often yields variable products, requires multi-step processing, often using highly corrosive environments, and usually involves a yield debit in the form of partly collapsed or blocked zeolite product. Few of the modified materials have the product quality of the starting sample because the process of modification involves partial destruction of the lattice and/or deposition of detrital reaction products within the pores of the structure. This usually results in the development of a secondary meso pore structure (Lohase et al, Zeolites, 4, p. 163 (1984)) which, although of some catalytic interested, will be less controlled and selective then the parent structure. Other methods of so called secondary synthesis using (NH.sub.4).sub.2 SiF.sub.6 in aqueous solution have also been demonstrated to yield higher silica zeolites (U.S. Pat. No. 4,503,023). Methods of directly synthesizing high silica faujasites, without such "secondary synthesis" treatments, would therefore be useful in optimizing both the zeolite product and the process for its production.
Although the disclosed composition is quite thermally stable in its own right because of its high silica content, that thermal stability makes the inventive composition particularly useful as a starting material for the dealumination processes described above. Since the number of aluminum atoms in the framework of the inventive composition is lower than in zeolite Y, removal of these atoms causes less framework metastability during dealumination, allowing the formation of near pure silica faujasites.
The objective of the present invention is to develop improved faujasite preparation methods yielding high silica materials, where the organic templates are not locked into the small cavities in the structure, but are instead present in the large "super cages" from which they can be readily removed without disruption and degradation of the host lattice. One such group of faujasite polymorphs are designated ECR-32 and ECR-4 (see U.S. Pat. Nos. 4,714,601, 4,965,059, and 4,931,267). The principal objective of this invention is to significantly improve the processes for making such materials.